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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Intercomparison of the Radio-Chronometric Ages of Plutonium-Certified Reference Materials with Distinct Isotopic Compositions

In this article, an intercomparison of the radio-chronometric ages of four distinct plutonium-certified reference materials varying in chemical form, isotopic composition, and period of production are presented. The cross-comparison of the different 234 U/ 238 Pu, 235 U/ 239 Pu, 236 U/ 240 Pu, and 241 Am/ 241 Pu model purification ages obtained at four independent analytical facilities covering a range of laboratory environments from bulk sample processing to clean facilities dedicated to nuclear forensic investigation of environmental samples enables a true assessment of the state-of-practice in “age dating capabilities” for nuclear materials. The analytical techniques evaluated used modern mass spectrometer instrumentation including thermal ionization mass spectrometers and inductively coupled plasma mass spectrometers for isotopic abundance measurements. Both multicollector and single collector instruments were utilized to generate the data presented here. Consensus values established in this study make it possible to use these isotopic standards as quality control standards for radio-chronometry applications. Results highlight the need for plutonium isotopic standards that are certified for 234 U/ 238 Pu, 235 U/ 239 Pu, 236 U/ 240 Pu, and 241 Am/ 241 Pu model purification ages as well as other multigenerational radio-chronometers such as 237 Np/ 241 Pu. Due to the capabilities of modern analytical instrumentation, analytical laboratories that focus on trace level analyses can obtain model ages with marginally larger uncertainties than laboratories that handle bulk samples. Lastly, when isotope ratio measurement techniques like thermal ionization mass spectrometry and inductively coupled plasma mass spectrometry with comparable precision are utilized, model purification ages with similar uncertainties are obtained.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. Furthermore, a separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effect of Natural Organic Matter on Plutonium Sorption to Goethite

For this research, the effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mg C ·L –1 and 50 mg C ·L –1 natural organic matter (NOM), 10 –9 –10 –10 M 238 Pu, and 0.1 g·L –1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increased Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. In conclusion, the results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Mechanisms of Plutonium Redox Reactions in Nitric Acid Solutions

Plutonium (Pu) exhibits a complex redox behavior in acidic solutions due to its ability to adapt a wide range of oxidation states typically from +3 to +6 and the tendency for dynamic interconversion between the oxidation states that depends upon electrochemical potential, acid concentration and coordination environments. In particular, the accurate redox speciation of Pu in nitric acid solutions and mapping the interconversion between the various oxidation states mechanistically is challenging due to overlapping chemical and electrochemical reactions leading to significant experimental uncertainties. The last several decades have seen the extensive use of spectroscopic methods to identify and characterize Pu solution species in the various oxidation states. However, dynamic redox mobility of Pu has led to discrepancies among the relevant spectral databases for Pu in nitric acid solutions. This work utilizes a combination of voltammetry and controlled-potential in-situ vis–NIR spectroelectrochemistry to overcome these challenges, and map the interconversion between Pu species in +3, +4, and +6 oxidation states. This allowed elucidation of the mechanisms of the involved redox reactions and an in-depth understanding of the relative stability of the Pu oxidation states through mapping of the Pu redox processes as a function of redox potentials and nitric acid concentrations. The NIR-spectroelectrochemistry studies used to spectroscopically map the redox speciation of Pu as a function of oxidation potentials with varying HNO3 concentrations allows a new perspective into the plutonium redox transformations.

Chatterjee, Sayandev↗
DOE OSTI2016

Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex

The reaction of formohydroxamic acid [NH(OH)CHO, FHA] with Pu III should result in stabilization of the trivalent oxidation state. However, slow oxidation to Pu IV occurs, which leads to formation of the dimeric plutonium(IV) formohydroxamate complex Pu 2 (FHA) 8 . In addition to being reductants, hydroxamates are also strong π-donor ligands. Furthermore, we show that formation of the Pu 2 (FHA) 8 dimer occurs via covalency between the 5f orbitals on plutonium and the π* orbitals of FHA – anions, which gives rise to a broad and intense ligand-to-metal charge-transfer feature. Here, time-dependent density functional theory calculations corroborate this assignment.

Color↗
DOE OSTI2026

Accessibility and Reactivity of Pentavalent Plutonium under Alkaline Conditions

Plutonium exhibits a particularly complex and rich aqueous chemistry due to a dynamic redox equilibrium that can result in the coexistence of four different oxidation states in aqueous solution. Within this equilibrium, pentavalent plutonium is among the most soluble and dominant oxidation states of Pu in neutral to alkaline aqueous solutions of relevance to environmental chemistries and the extreme chemical environments encountered in high-level radioactive wastes. Despite this, the fundamental chemistry of Pu­(V) under such conditions remains poorly understood. Here, in this study, we demonstrate the redox accessibility of Pu­(V) in alkaline media based on the observations of an electrochemically reversible Pu­(VI/V) couple at E 1/2 = 0.19 V vs Hg/HgO (0.29 V vs NHE), allowing us to electrolytically generate Pu­(V) in alkaline solution. These Pu­(V) solutions remained stable under ambient conditions for at least 9 days before precipitation of crystalline Na 2 [Pu V O 2 (OH) 3 ]·2H 2 O, the first structurally characterized Pu­(V) hydroxide. The modest potential of the Pu­(VI/V) redox couple allowed us to reproduce Na 2 [Pu V O 2 (OH) 3 ]·2H 2 O synthetically as well as isolate two additional novel Pu­(V)-bearing hydroxide phases Na­[Pu V O 2 (OH) 2 (H 2 O)]·2.5H 2 O and K 2 [Pu V O 2 (OH) 3 ]·2H 2 O as single crystals from alkaline reactions under mild hydrothermal conditions (<200 °C) using Na 2 O 2 and KO 2 as reductants. This reactivity is rationalized and informed by our electrochemical measurements. The properties of the Pu­(V) solids were further characterized by using vibrational and optical spectroscopy.

Kravchuk, Dmytro V. [Argonne National Laboratory (↗
DOE OSTI2024

Plutonium oxide melt structure and covalency

Advances in nuclear power reactors include the use of mixed oxide fuel, containing uranium and plutonium oxides. The high-temperature behaviour and structure of PuO 2-x above 1,800 K remain largely unexplored, and these conditions must be considered for reactor design and planning for the mitigation of severe accidents. Here, in this study, we measure the atomic structure of PuO 2-x through the melting transition up to 3,000 +/- 50 K using X-ray scattering of aerodynamically levitated and laser-beam-heated samples, with O/Pu ranging from 1.57 to 1.76. Liquid structural models consistent with the X-ray data are developed using machine-learned interatomic potentials and density functional theory. Molten PuO 1.76 contains some degree of covalent Pu-O bonding, signalled by the degeneracy of Pu 5f and O 2p orbitals. The liquid is isomorphous with molten CeO 1.75 , demonstrating the latter as a non-radioactive, non-toxic, structural surrogate when differences in the oxidation potentials of Pu and Ce are accounted for. These characterizations provide essential constraints for modelling pertinent to reactor safety design. The molten structure of plutonium oxide-a component of mixed oxide nuclear fuels-is measured, showing some degree of covalent bonding. Its atomic structure is similar to that of cerium oxide, which could be a non-radioactive structural surrogate.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Laboratory-based characterization of plutonium in soil particles using micro-XRF and 3D confocal XRF

The investigation of plutonium (Pu) in a soil matrix is of interest in safeguards, nuclear forensics, and environmental remediation activities. The elemental composition of two plutonium contaminated soil particles was characterized nondestructively using a pair of micro X-ray fluorescence spectrometry (micro-XRF) techniques including high resolution X-ray (hiRX) and 3D confocal XRF. The three dimensional elemental imaging capability of confocal XRF permitted the identification two distinct Pu particles within the samples: one external to the Ferich soil matrix and another co-located with Cu within the soil matrix. The size and morphology of the particles was assessed with X-ray transmission microscopy and micro X-ray computed tomography (micro-CT) providing complementary morphological information. Limits of detection for a 30 μm Pu particle are <10 ng for each of the XRF techniques. Ultimately, this study highlights the capability for lab-based, nondestructive, spatially resolved characterization of heterogeneous matrices on the micrometer scale with nanogram sensitivity.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold

Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [M IV (TREN TIPS )(Cl)] [An = Np, Pu; TREN TIPS = {N(CH 2 CH 2 NSiPr i 3 ) 3 } 3 ] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [M III (TREN TIPS )]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Unveiling the covalency of versatile Pu(iii)-N bonds in a unique plutonium(iii) complex

A trivalent plutonium–pyrazinyl–tetrazolate complex Na 2 [Pu(Hdtp)(dtp) 2 (H 2 O) 4 ]·9H 2 O (Pu_dtp, H 2 dtp = 2,3-di-1H-tetrazol-5-ylpyrazine) was synthesized through metathesis reaction of plutonium bromide and Na 2 (dtp)·2H 2 O in water. This structure is particularly notable among complexes formed by trivalent f-elements and the dtp 2− ligand in aqueous media. In contrast to other trivalent f-elements, including all Ln 3+ (with the exception of Pm 3+ ) and Cm 3+ , preferentially coordinated with eight water molecules rather than the nitrogen donors of the dtp 2− ligand, Pu 3+ exhibits a distinct affinity for nitrogen coordination. This observation provides strong evidence that the 5f electrons in Pu 3+ are more delocalized than other studied trivalent f-elements. In Pu_dtp, three distinct Pu(III)–N bonds are present: one Pu(III)–N5 from pyrazinyl, one Pu(III)–N4 from the least electronegative nitrogen in the tetrazolate, and three Pu(III)–N1/N2/N3 from the most electronegative nitrogens in the tetrazolate. Experimental Pu(III)–N bond lengths, Wiberg bond indices (WBI), natural localized molecular orbitals (NLMO), quantum theory of atoms in molecules (QTAIM), and energy decomposition analysis (EDA), reveal a covalency trend: Pu(III)–N from the most electronegative nitrogen in tetrazolate > Pu(III)–N from the least electronegative nitrogen in tetrazolate > Pu(III)–N from pyrazinyl. This trend arises from the increased negative charge on the most electronegative nitrogen atoms in the tetrazolate ring, enhancing electrostatic Pu–N1/N2/N3 interactions. These stronger electrostatic interactions lead to shorter bond lengths, thereby enhancing orbital overlap and greater covalency, compared to the less electronegative nitrogen in tetrazolate (Pu–N4) and the neutral pyrazinyl nitrogen (Pu–N5).

Bai, Zhuanling [Colorado School of Mines, Golden, ↗
DOE OSTI2024

Analysis of differential scanning calorimetry data for aged plutonium

Differential scanning calorimetry data for samples of a 52 year old plutonium alloy with 3.3 at. % Ga that were heated beyond the melting point is analyzed using transition state theory to find activation energies for the δ to ε and ε to liquid phase transitions. A Bayesian statistical method involving a Gaussian process model is used to find mean values and confidence intervals for the activation energies. The activation energy for the δ to ε phase transition increases by 3.3 ± 3.8% per decade, relative to the case when all age related plutonium lattice point defects have been removed through annealing. The corresponding increase in activation energy for the ε to liquid transition is shown to be 7.1 ± 1.8% per decade. It is postulated that the change in activation energy with age for both phase transitions is caused, in part, by the accumulation of the same type of lattice point defects associated with the observed increase in elastic bulk modulus over time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A Conversion Proposal for Iran's IR-40 Reactor with Reduced Plutonium Production

Our article examines possible modifications of Iran’s IR-40 (Arak) heavy-water reactor that would limit its plutonium production without compromising its usefulness for civilian purposes. The proposed modifications only involve the fuel composition, avoid changes to the fuel and core geometry, and therefore have the advantage of minimizing the overall complexity and cost of conversion as well as shortening the time period required to implement these modifications. The suggested changes would significantly reduce the reactor’s production of plutonium from 7–9 kilograms to less than 1 kilogram per year. This article also examines key safety parameters, medical isotope production rates, and uranium resource requirements for all modifications considered. Our analysis is relevant beyond the case of Iran’s Arak reactor and may provide some future guidance for converting other heavy-water reactors that continue to operate today.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2025

Estimating Potential Tritium and Plutonium Production in North Korea’s Experimental Light Water Reactor

Our work explores North Korea's 100 MW-th Experimental Light Water Reactor (ELWR) and its potential contributions to the country's nuclear weapons program. Built at the Yongbyon Nuclear Research Center, the ELWR began operations in October 2023 and represents North Korea's first attempts at a light-water reactor using domestically-enriched, ceramic fuel. Our study examines possible configurations for energy, tritium, and tritium-plutonium co-production. Assuming a single-batch core, the ELWR can be used to annually produce 48-82 grams of tritium, which can supply 2-4 new boosted warheads each year, up to a maximum arsenal of 88-150 warheads total. Concurrent production of tritium and weapon-grade plutonium is also possible but requires reprocessing of spent ceramic fuel. Furthermore, these findings underscore how North Korea's nuclear capabilities may be advanced through the ELWR's dual-use potential.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Some Considerations for Chelation Treatment and Surgical Excision Following Incorporation of Plutonium in Wounds

After a plutonium-contaminated wound, the role of an internal dosimetrist is to inform the patient and the physician of the dosimetric considerations. The doses averted due to medical treatments (excision or chelation) are higher if the treatments are administered early; therefore, the internal dosimetrist needs to rely on limited information on wound counts and process knowledge for advising the physician. For this study, several wound cases in the literature were reviewed to obtain estimates of the efficacies of surgical excision and chelation treatment after plutonium-contaminated wounds. The dose coefficients calculated by coupling the NCRP 156 wound model with the systemic model were used to derive the decision guidelines that may indicate medical treatment based on 1) the concept of saved doses proposed by the NCRP 156 wound model, 2) the limits recommended by the CEC/DOE guidebook, and 3) the Clinical Decision Guidelines proposed in NCRP Report No. 161. These guidelines by themselves, however, are of limited use for several reasons, including 1) large uncertainties associated with wound measurements, 2) exposure to forms of radionuclides that cannot be assigned to a single category in the NCRP 156 framework, 3) inability of the NCRP 156 model to explain some of the wound cases in the literature, 4) neglect of the local doses to the wound site and the pathophysiological response of the tissue, 5) poorly understood relationship between effective doses and risks of late health effects, and 6) disregard of the psychological aspects of radionuclide intake.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2020

Electronic correlation induced expansion of Fermi pockets in δ-plutonium

Plutonium is a critically important material as the behavior of its 5f electrons stands midway between the metalliclike itinerant character of the light actinides and localized atomic-core-like character of the heavy actinides. The δ phase of plutonium (δ-Pu), whereas still itinerant, has a large coherent Kondo peak and strong electronic correlations coming from its near-localized character. Here, using sophisticated Gutzwiller wave function and dynamical mean-field theory correlated theories, we study the Fermi surface and associated mass renormalizations of δ-Pu together with calculations of the de Haas–van Alphen frequencies. We find a large (~200%) correlation induced volume expansion in both the hole and the electron pockets of the Fermi surface in addition to an intermediate mass enhancement. All of the correlated electron theories predict, approximately, the same hole pocket placement in the Brillouin zone, which is different from that obtained in conventional density-functional band-structure theory, whereas the electron pockets from all theories are in, roughly, the same place.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Scanning transmission x-ray microscopy (STXM) of plutonium oxide

Scanning transmission x-ray microscopy was used to examine plutonium oxide particles formed by the corrosion of δ-phase plutonium alloy under high-humidity conditions. O K-edge spectra collected from eight distinct particles displayed significant spectral differences, revealing heterogeneity in oxidation states within a single sample batch. Here, this variation suggests complex chemical environments and formation histories, which are important considerations for nuclear forensic investigations. These findings highlight both the potential of synchrotron-based x-ray microscopy for nondestructive, high-resolution analysis of nuclear materials and the need for expanded reference datasets to improve the interpretation and forensic utility of such measurements.

organic↗
DOE OSTI2017

Integrated Nondestructive Assay Systems to Estimate Plutonium in Spent Fuel Assemblies

An integrated nondestructive assay (NDA) system combining active (neutron generator) and passive neutron detection and passive gamma (PG) detection is being analyzed in order to estimate the amount of plutonium, verify initial enrichment, burnup, and cooling time, and detect partial defects in a spent fuel assembly (SFA). Active signals are measured using the differential die-away (DDA), delayed neutron (DN), and delayed gamma (DG) techniques. Passive signals are measured using total neutron (TN) counts and both gross and spectral resolved gamma counts. To quantify how a system of several NDA techniques is expected to perform, all of the relevant NDA techniques listed above were simulated as a function of various reactor conditions such as initial enrichment, burnup, cooling time, assembly shuffling pattern, reactor operating conditions (including temperature, pressure, and the presence of burnable poisons) by simulating the NDA response for five sets of light water reactor assemblies. In this study, we compare the performance of several exploratory model-fitting options (including neural networks, adaptive regression with splines, iterative bias reduction smoothing, projection pursuit regression, and regression with quadratic terms and interaction terms) to relate data simulated with measurement and model error effects from various subsets of the NDA techniques to the total Pu mass. Isotope masses for SFAs and expected detector responses (DRs) for several NDA techniques are simulated using MCNP, and the DRs become inputs to the fitting process. Such responses include eight signals from DDA, one from DN, one from TN, and up to seven from PG; the DG signal will be examined separately. Results are summarized using the root-mean-squared estimation error for plutonium mass in held-out subsets of the data for a range of model and measurement error variances. Different simulation assumptions lead to different spent fuel libraries relating DRs to Pu mass. Some results for training with one library and testing with another library are also given.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2017

Sensitivity and Uncertainty Analysis of Plutonium and Cesium Isotopes in Modeling of BR3 Reactor Spent Fuel

Nuclear forensics has a broad task to characterize recovered nuclear or radiological material and interpret the results of investigation. One approach to isotopic characterization of nuclear material obtained from a reactor is to chemically separate and perform isotopic measurements on the sample and verify the results with modeling of the sample history, for example, operation of a nuclear reactor. The major actinide plutonium and fission product cesium are commonly measured signatures of the fuel history in a reactor core. This study investigates the uncertainty of the plutonium and cesium isotope ratios of a fuel rod discharged from a research pressurized water reactor when the location of the sample is not known a priori. A sensitivity analysis showed overpredicted values for the 240 Pu/ 239 Pu ratio toward the axial center of the rod and revealed a lower probability of the rod of interest (ROI) being on the periphery of the assembly. The uncertainty analysis found the relative errors due to only the rod position and boron concentration to be 17% to 36% and 7% to 15% for the 240 Pu/ 239 Pu and 137 Cs/ 135 Cs ratios, respectively. Lastly, this study provides a method for uncertainty quantification of isotope concentrations due to the location of the ROI. Similar analyses can be performed to verify future chemical and isotopic analyses.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗